US11282622B2 - Ferrite composition and multilayer electronic component - Google Patents

Ferrite composition and multilayer electronic component Download PDF

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US11282622B2
US11282622B2 US16/727,553 US201916727553A US11282622B2 US 11282622 B2 US11282622 B2 US 11282622B2 US 201916727553 A US201916727553 A US 201916727553A US 11282622 B2 US11282622 B2 US 11282622B2
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US20200243239A1 (en
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Takeshi Shibayama
Takashi Suzuki
Takahiro Sato
Kenji KOMORITA
Tatsuro Suzuki
Yukio Takahashi
Hiroyuki TANOUE
Yasuhiro Ito
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TDK Corp
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/85—Intergranular or grain boundary phases

Definitions

  • the present invention relates to a ferrite composition and a multilayer electronic component.
  • Examples of the noise removal products include winding-wire type ferrite inductors and multilayer type ferrite inductors.
  • winding-wire type ferrite inductors are employed in view of height in noise removal characteristics.
  • noise removal characteristics equal to or greater than those of winding-wire type ferrite inductors are also demanded for multilayer type ferrite inductors.
  • Patent Document 1 and Patent Document 2 disclose a ferrite composition having excellent characteristics by controlling its composition and a multilayer electronic component.
  • Patent Document 1 JP5582279 (B2)
  • Patent Document 2 JP2013060332 (A)
  • the present invention has been achieved under such circumstances. It is an object of the invention to provide a ferrite composition or so having improved inductance characteristics or so.
  • a ferrite composition according to the present invention includes a main component and a sub-component, wherein
  • the main component includes 10.0 to 38.0 mol % of a Fe compound in terms of Fe 2 O 3 , 3.0 to 11.0 mol % of a Cu compound in terms of CuO, 39.0 to 80.0 mol % (excluding 39.0 mol %) of a Zn compound in terms of ZnO, and a balance of a Ni compound, and
  • the sub-component includes 10.0 to 23.0 parts by weight of a Si compound in terms of SiO 2 , 0 to 3.0 parts by weight (including 0 parts by weight) of a Co compound in terms of Co 3 O 4 , and 0.1 to 3.0 parts by weight of a Bi compound in terms of Bi 2 O 3 with respect to 100 parts by weight of the main component.
  • the ferrite composition according to the present invention has the above features and thereby has improved inductance characteristics, high resistivity and permeability ⁇ ′, and favorable DC superposition characteristics and AC resistance.
  • permeability ⁇ ′ is a real part of complex permeability.
  • the sub-component may include 0.1 to 1.0 parts by weight of a Co compound in terms of Co 3 O 4 .
  • the ferrite composition according to the present invention may be composed of a main phase composed of spinel ferrite, a first sub-phase including a Zn 2 SiO 4 phase, and a grain boundary phase including a SiO 2 phase.
  • the ferrite composition according to the present invention may further include a second sub-phase including a SiO 2 phase.
  • a multilayer electronic component according to the present invention includes a coil conductor and ceramic layers,
  • the ceramic layers are composed of the above-mentioned ferrite composition.
  • the electronic component according to the present invention can demonstrate noise removal characteristics equal to or greater than those of a wire-winding type coil device even though the electronic component according to the present invention is a multilayer type electronic component.
  • FIG. 1 is an internally transparent perspective view of a multilayer chip coil as an electronic component according to an embodiment of the present invention.
  • FIG. 2 is an internally transparent perspective view of a multilayer chip coil as an electronic component according to another embodiment of the present invention.
  • FIG. 3A is an EPMA image of a ferrite composition according to the present invention.
  • FIG. 3B is a schematic view of a ferrite composition according to the present invention.
  • FIG. 4A is a Si element mapping image of a ferrite composition according to the present invention.
  • FIG. 4B is a Zn element mapping image of a ferrite composition according to the present invention.
  • FIG. 4C is a Ni element mapping image of a ferrite composition according to the present invention.
  • FIG. 5 is a schematic view of a ferrite composition according to the present invention.
  • a multilayer chip coil 1 as an electronic component includes a chip body 4 containing ceramic layers 2 and internal electrode layers 3 alternately laminated in the Y-axis direction.
  • Each of the internal electrode layers 3 has a square ring shape, a C shape, or a U shape.
  • the internal electrode layers 3 are spirally connected by a stepped electrode or a through hole electrode (not shown) for connecting internal electrodes going through the adjacent ceramic layers 2 and constitute a coil conductor 30 .
  • Terminal electrodes 5 and 5 are formed on both ends of the chip body 4 in the Y-axis direction. Each of the terminal electrodes 5 is connected with an end of a terminal-connection through hole electrode 6 going through the laminated ceramic layers 2 . The terminal electrodes 5 and 5 are connected with both ends of the coil conductor 30 forming a closed-magnetic-path coil (winding wire pattern).
  • the ceramic layers 2 and the internal electrode layers 3 are laminated in the Y-axis direction, and the end surfaces of the terminal electrodes 5 and 5 are parallel to the X-axis and the Z-axis.
  • the X-axis, the Y-axis, and the Z-axis are perpendicular to each other.
  • the winding axis of the coil conductor 30 substantially corresponds to the Y-axis.
  • the chip body 4 has any outer shape and size that can approximately be determined based on purposes, but normally has a substantially rectangular parallelepiped shape with, for example, a length of 0.15 to 0.8 mm in the X-axis direction, a length of 0.3 to 1.6 mm in the Y-axis direction, and a length of 0.1 to 1.0 mm in the Z-axis direction.
  • the ceramic layers 2 have any thickness between electrodes and any base thickness.
  • the ceramic layers 2 can have a thickness between electrodes (an interval between the internal electrode layers 3 and 3 ) of about 3 to 50 ⁇ m and a base thickness (a length of the terminal-connection through hole electrode 6 in the Y-axis direction) of about 5 to 300 ⁇ m.
  • the terminal electrodes 5 are not limited and are formed by attaching a conductive paste whose main component is Ag, Pd, etc. onto the outer surface of the body 4 , firing the paste, and subjecting it to an electric plating.
  • the electric plating can be carried out using Cu, Ni, Sn, etc.
  • the coil conductor 30 contains Ag (including an Ag alloy) and is composed of Ag alone, Ag—Pd alloy, or the like.
  • the coil conductor 30 can contain a sub-component of Zr, Fe, Mn, Ti, and an oxide thereof.
  • the ceramic layers 2 are composed of a ferrite composition according to an embodiment of the present invention.
  • the ferrite composition is explained in detail.
  • the ferrite composition according to the present embodiment contains a main component of a Fe compound, a Cu compound, a Zn compound, and a Ni compound.
  • the Fe compound may include Fe 2 O 3
  • the Cu compound may include CuO
  • the Zn compound may include ZnO
  • the Ni compound may include NiO.
  • the amount of the Fe compound is 10.0 to 38.0 mol %, preferably 20.7 to 34.3 mol %, in terms of Fe 2 O 3 .
  • the amount of the Fe compound is large, DC superposition characteristics and resistivity are easy to decrease.
  • the amount of the Fe compound is small, permeability ⁇ ′ is easy to decrease.
  • the amount of the Cu compound is 3.0 to 11.0 mol %, preferably 3.6 to 5.9 mol %, in terms of CuO.
  • the amount of the Cu compound is large, DC superposition characteristics are easy to decrease, AC resistance is easy to increase, and resistivity is easy to decrease.
  • the amount of the Cu compound is small, sinterability deteriorates (particularly, sintering density in low temperature sintering is easy to decrease), resistivity is easy to decrease due to deterioration of sinterability, and permeability ⁇ ′ is easy to decrease.
  • the amount of the Zn compound is 39.0 to 80.0 mol % (excluding 39.0 mol %), preferably 46.2 to 61.8 mol %, in terms of ZnO.
  • the amount of the Zn compound is large, permeability ⁇ ′ is easy to decrease.
  • the amount of the Zn compound is small, DC superposition characteristics are easy to decrease, and AC resistance is easy to increase.
  • the balance of the main component is composed of the Ni compound.
  • the amount of the Ni compound is preferably 47.0 mol % or less, more preferably less than 40.0 mol %, in terms of NiO.
  • the amount of the Ni compound has any lower limit, such as 0.1 mol %. When the amount of the Ni compound is large, DC superposition characteristics are easy to decrease, and AC resistance is easy to increase.
  • the ferrite composition according to the present embodiment includes a sub-component of a Si compound and a Bi compound and may further include a Co compound.
  • the amount of the Si compound is 10.0 to 23.0 parts by weight, preferably 14.8 to 22.0 parts by weight, in terms of SiO 2 .
  • the amount of the Si compound is large, sinterability deteriorates, and permeability ⁇ ′ is easy to decrease.
  • the amount of the Si compound is small, DC superposition characteristics are easy to decrease, and AC resistance is easy to increase.
  • the amount of the Co compound is 0 to 3.0 parts by weight (including 0 parts by weight) in terms of Co 3 O 4 . That is, the Co compound may not be contained.
  • the amount of the Co compound is preferably 0 to 1.0 parts by weight, but may be 0.1 to 1.0 parts by weight.
  • permeability ⁇ ′ is easy to decrease. The smaller the Co content is, the smaller the loss is particularly in using the ferrite composition at high frequency.
  • the amount of the Bi compound is 0.1 to 3.0 parts by weight, preferably 1.2 to 3.0 parts by weight, in terms of Bi 2 O 3 .
  • the amount of the Bi compound is large, resistivity is easy to decrease, DC superposition characteristics are easy to decrease, AC resistance is easy to increase, and permeability ⁇ ′ is easy to decrease.
  • the amount of the Bi compound is small, resistivity is easy to decrease, a sufficient sinterability is hard to be obtained (particularly, density is easy to decrease at low temperature sintering), and permeability ⁇ ′ is easy to decrease.
  • the Bi compound has an effect of promoting the generation of Zn 2 SiO 4 in sintering step.
  • the effect of promoting the generation of Zn 2 SiO 4 is particularly large.
  • (the amount of the Co compound in terms of Co 3 O 4 )/(the amount of the Si compound in terms of SiO 2 ) (hereinafter, simply referred to as “Co/Si”) is 0 to 0.300 in weight ratio. More preferably, Co/Si is 0.005 to 0.100. Even if the amount of the Co compound and the amount of the Si compound are within the above-mentioned ranges, permeability ⁇ ′ is easy to decrease when Co/Si is high, and density is easy to decrease when Co/Si is low.
  • the amount of each constituent of the main component and the sub-component does not substantially change from a step of the raw material powder to a step after firing.
  • the composition range of each constituent of the main component is controlled to the above-mentioned range, and the sub-component of the Si compound, the Co compound, and the Bi compound is additionally contained within each of the above-mentioned ranges. It is consequently possible to obtain a ferrite composition having a favorable sinterability, high resistivity and permeability and favorable DC superposition characteristics and AC resistance.
  • the ferrite composition according to the present embodiment can be sintered at about 900° C., which is equal to or lower than the melting point of Ag (used as the internal electrodes), and is thereby applicable to various purposes.
  • the ferrite composition according to the present embodiment may include an additional component of manganese oxide (e.g., Mn 3 O 4 ), zirconium oxide, tin oxide, magnesium oxide, glass compound, etc. as long as the effects of the present invention are not disturbed.
  • the amount of the additional component is not limited and is, for example, about 0.05 to 1.0 parts by weight with respect to 100 parts by weight of the main component.
  • the amount of magnesium oxide is preferably 0.5 parts by weight or less (including zero).
  • the amount of magnesium oxide is 0.5 parts by weight or less, the reaction between MgO and SiO 2 is prevented, and the following first sub-phase composed of Zn 2 SiO 4 phase is easily generated.
  • the ferrite composition according to the present embodiment may contain an oxide of inevitable impurity elements.
  • the inevitable impurity elements are elements other than the above-mentioned elements. More specifically, the inevitable impurities are C, S, Cl, As, Se, Br, Te, I, Li, Na, Mg, Al, Ca, Ga, Ge, Sr, Cd, In, Sb, Ba, Pb, Sc, Ti, V, Cr, Y, Nb, Mo, Pd, Ag, Hf, Ta, etc.
  • the oxide of the inevitable impurity elements may be contained as long as its amount is about 0.05 parts by weight or less in the ferrite composition.
  • the Al content is 0.05 parts by weight or less with respect to 100 parts by weight of the main component in terms of Al 2 O 3 , sinterability and resistivity are easy to improve.
  • the ferrite composition according to the present embodiment has the above-mentioned composition and a composite structure as shown in FIG. 3A and FIG. 3B .
  • FIG. 3A is an observation result of a ferrite composition 11 according to the present embodiment (No. 2 mentioned below) at a magnification of 20000 times by STEM-EDS.
  • FIG. 3B is a schematic view of FIG. 3A .
  • a favorable ferrite composition 11 contains a main phase 12 composed of spinel ferrite and further contains a first sub-phase 14 a composed of Zn 2 SiO 4 phase and a second sub-phase 14 b composed of SiO 2 phase.
  • a grain boundary phase 16 composed of SiO 2 phase is contained among the phases (the main phase 12 , the first sub-phase 14 a , and the second sub-phase 14 b ).
  • the second sub-phase 14 b composed of SiO 2 phase may not be contained, but is preferably contained.
  • the first sub-phase 14 a other elements, such as Ni, Cu, and Co, may be contained and may be solid-soluted in Zn 2 SiO 4 .
  • the second sub-phase 14 b may contain other elements, such as Fe and Ni.
  • the grain boundary phase 16 contains Bi 2 O 3 more than the main phase 12 does. Incidentally, the second sub-phase 14 b and the grain boundary phase 16 are provisionally distinguished in FIG. 3A and FIG. 3B .
  • the second sub-phase 14 b is a portion where a content ratio of SiO 2 is larger than that of Bi 2 O 3 by molar ratio
  • the grain boundary phase 16 is a portion where a content ratio of SiO 2 is equal to or lower than that of Bi 2 O 3 by molar ratio.
  • the second sub-phase 14 b and the grain boundary phase 16 can accurately be distinguished by the following observation using a STEM-EDS at a higher magnification.
  • the first sub-phase 14 a composed of Zn 2 SiO 4 phase
  • the second sub-phase 14 b containing SiO 2 and the grain boundary phase 16 containing SiO 2 have a small thermal expansion coefficient.
  • each phase having a small thermal expansion coefficient applies a tensile stress to the main phase 12 having a large thermal expansion coefficient. This improves inductance characteristics of a coil device using the ferrite composition 11 .
  • the proportion of the sub-phases 14 to the total of the main phases 12 , the sub-phases 14 (whose composition is different from that of the main phase 12 ), and the grain boundary phases 16 is larger than that of conventional ferrite compositions.
  • the total area of the sub-phases 14 is preferably 50% or more and 70% or less with respect to 100% of the total area of the main phases 12 , the sub-phases 14 , and the grain boundary phases 16 .
  • the ratio of the first sub-phase 14 a composed of Zn 2 SiO 4 phase is preferably larger than that of the second sub-phase 14 b in the sub-phase 14 .
  • the ratio of the first sub-phase 14 a may be larger than that of the main phase 12 .
  • the ferrite composition 11 has a three-dimensional structure where the main phases 12 and the sub-phases 14 are tangled. Thus, the ferrite composition 11 has a complex structure where the main phases 12 (magnetic phases) and the sub-phases 14 (non-magnetic phases) are dispersed.
  • the ferrite composition 11 has a three-dimensional magnetic path structure, and an effect of reducing magnetic saturation by minor multiple gaps (dispersion gap effect) is large. Since the dispersion gap effect is large, the coil device composed of the ferrite composition 11 has improved inductance characteristics particularly when used with large electric current, a high permeability ⁇ ′, and favorable DC superposition characteristics and AC resistance.
  • the area of the first sub-phases 14 a is 30% or more and 70% or less.
  • the area of the second sub-phases 14 b is 0.5% or more and 10% or less.
  • the area of the main phases 12 is preferably 30% or more and 50% or less, and the area of the grain boundary phases 16 is preferably 0.1% or more and 4.0% or less.
  • Zn 2 SiO 4 phase is a phase containing Zn 2 SiO 4
  • SiO 2 phase is a phase where a content ratio of SiO 2 is higher than that of the main phases
  • Bi 2 O 3 phase is a phase where a content ratio of Bi 2 O 3 is higher than that of the main phases.
  • FIG. 4A to FIG. 4C are a Si element mapping image, a Zn element mapping image, and a Ni element mapping image, respectively, of the ferrite composition 11 (No. 2) according to the present embodiment obtained using a STEM-EDS at a magnification of 100000 times.
  • FIG. 5 is a schematic view of FIG. 4A to FIG. 4C .
  • any method can be used for confirming whether the sub-phases 14 in FIG. 4A to FIG. 4C and FIG. 5 are the first sub-phases 14 a or the second sub-phases 14 b.
  • the grain boundary phase 16 composed of SiO 2 phase is present among the phases (the main phase 12 , the first sub-phase 14 a , and the second sub-phase 14 b ), and there can be seen a core-shell structure where a shell containing SiO 2 surrounds a core (the main phase or the sub-phase).
  • the concentration distribution of Zn may be uniform, but the concentration of Zn is preferably comparatively high in an outer part of the main phase 12 close to the grain boundary phase 16 .
  • the concentration of Ni is preferably comparatively low, and the concentration of Si is preferably comparatively high.
  • the mapping image of Zn and the mapping image of Ni are observed, the above-mentioned concentration distribution of the main phase 12 can be confirmed by a gradation generated in the main phase 12 .
  • the above-mentioned tensile stress is considered to be transmitted efficiently.
  • the grain boundary phase 16 also contains Bi 2 O 3 .
  • the fact that the grain boundary phase 16 is Bi 2 O 3 phase and SiO 2 phase can be confirmed by, for example, a line analysis of a portion passing through the main phase 12 and the grain boundary phase 16 using a STEM-EDS.
  • the ferrite composition 11 contains the grain boundary phases 16 (SiO 2 phase)
  • the ratio of the grain boundary phases 16 is larger than that of grain boundary phases of conventional ferrite compositions. This means that the grain boundary phases 16 are thicker than those of conventional ferrite compositions.
  • the grain boundary phases 16 (SiO 2 phase) whose thermal expansion coefficient is different from that of the main phases 12 , are contained and cover each phase, and a tensile stress is thereby applied from the grain boundary phases 16 to each phase.
  • the ferrite composition 11 has improved inductance characteristics, high resistivity and permeability and favorable DC superposition characteristics and AC resistance.
  • the area of the grain boundary phases 16 is preferably 0.1% or more and 4.0% or less with respect to 100% of the total area of the main phases 12 , the sub-phases 14 , whose thermal expansion coefficient is different from that of the main phases 12 , and the grain boundary phases 16 in a STEM-EDS image that is large enough to observe the main phases 12 at a magnification of 20000 times or more.
  • main phases 12 and the sub-phases 14 of the ferrite composition 11 according to the present embodiment are crystal grains, they preferably have an average crystal grain size of 0.2 to 1.5 ⁇ m.
  • the average crystal grain size is measured by any method, such as XRD.
  • the presence of the Zn 2 SiO 4 phase can also be confirmed by X-ray diffraction.
  • An X-ray diffraction intensity of a ferrite composition is measured by an X-ray diffraction device, and a peak intensity I A of ( 311 ) plane of spinel-type ferrite and a peak intensity I B of ( 113 ) plane of Zn 2 SiO 4 in the ferrite composition 11 are measured.
  • the amount of Zn 2 SiO 4 phase is a value (I B /I A ) obtained by dividing the intensity I B by the intensity I A .
  • the X-ray diffraction intensity is a value obtained by subtracting background from the intensity shown by the X-ray diffraction device.
  • the amount of Zn 2 SiO 4 (I B /I A ) is 0.05 or more.
  • the amount of Zn 2 SiO 4 has any upper limit, but I B /I A is preferably 0.6 or less.
  • Starting raw materials raw materials of the main component and raw materials of the sub-component
  • the starting raw materials preferably have an average grain size of 0.05 to 1.0 ⁇ m.
  • the raw materials of the main component can be iron oxide ( ⁇ -Fe 2 O 3 ), copper oxide (CuO), nickel oxide (NiO), zinc oxide (ZnO), a composite oxide, etc.
  • This composite oxide is, for example, zinc silicate (Zn 2 SiO 4 ).
  • materials to be the above-mentioned oxides by firing include metal single substance, carbonate, oxalate, nitrate, hydroxide, halide, and organometallic compound.
  • the raw materials of the sub-component can be silicon oxide, bismuth oxide, and cobalt oxide.
  • the oxide to be the raw materials of the sub-component is not limited and can be a composite oxide or so. This composite oxide is, for example, zinc silicate (Zn 2 SiO 4 ).
  • Zn 2 SiO 4 zinc silicate
  • Co 3 O 4 (a form of cobalt oxide) is favorable as a raw material of the cobalt compound because Co 3 O 4 is easily stored and handled and is stable in terms of valence even in the air.
  • iron oxide, copper oxide, nickel oxide, and zinc oxide are mixed to obtain a raw material mixture.
  • zinc oxide may not be added at this stage and may be added along with zinc silicate after the raw material mixture is calcined.
  • a part of the raw materials of the sub-component may be mixed with the raw materials of the main component.
  • the existence ratio of the main phases, the first sub-phases, the second sub-phases, and the grain boundary phases can be controlled by appropriately controlling the kind and ratio of the raw materials contained in the raw material mixture and the kind and ratio of the raw materials added after the raw material mixture is calcined.
  • the mixing is carried out by any method, such as a wet mixing using a ball mill and a dry mixing using a dry mixer.
  • the raw material mixture is calcined to obtain a calcined material.
  • the calcination causes thermal decomposition of the raw materials, homogenization of the components, generation of ferrite, disappearance of ultrafine powder by sintering, and grain growth to appropriate grain size and is carried out for conversion of the raw material mixture into a form suitable to the following steps.
  • the calcination is normally carried out in the atmosphere (air), but may be carried out in an atmosphere whose partial pressure of oxygen is lower than that of the atmosphere.
  • the calcined material is mixed with silicon oxide, bismuth oxide, cobalt oxide, zinc silicate, etc. to be the raw materials of the sub-component so as to manufacture a mixed calcined material.
  • the larger the amount of zinc silicate added at this stage is, the more easily the existence ratio of the first sub-phases (Zn 2 SiO 4 phases) becomes high.
  • the larger the amount of zinc silicate added at this stage is, the more easily the above-mentioned concentration distribution is generated in the main phases 12 .
  • the smaller the amount of Zn in the calcined material the more easily the existence ratio of the grain boundary phases (SiO 2 phases and Bi 2 O 3 phases) becomes high.
  • the mixed calcined material is pulverized to obtain a pulverized calcined material.
  • the pulverization is carried out for crushing the aggregation of the mixed calcined material and turning it into a powder having an appropriate sinterability.
  • a rough pulverization is carried out, and a wet pulverization is thereafter carried out using a ball mill, an attritor, or the like.
  • the wet pulverization is carried out until the pulverized calcined material preferably has an average grain size of about 0.1 to 1.0
  • the multilayer chip coil 1 shown in FIG. 1 can be manufactured by a normal method. That is, the chip body 4 can be formed in such a manner that an internal-electrode paste containing Ag or so and a ferrite paste obtained by kneading the pulverized calcined material with a binder and a solvent are alternately printed and laminated and are thereafter fired (printing method). Instead, the chip body 4 may be formed in such a manner that the internal-electrode paste is printed on green sheets manufactured using the ferrite paste, and the green sheets are laminated and fired (sheet method). In anyway, the terminal electrodes 5 are formed by firing, plating, or the like after the chip body is formed.
  • each amount of the binder and the solvent in the ferrite paste is not limited.
  • the amount of the binder can be about 1 to 10 wt %, and the amount of the solvent can be about 10 to 50 wt %.
  • the ferrite paste may contain 10 wt % or less of dispersant, plasticizer, dielectric, insulator, etc.
  • the internal-electrode paste containing Ag or so can be manufactured in a similar manner.
  • the firing conditions are not limited, but when the internal electrode layers contain Ag or so, the firing temperature is preferably 930° C. or less, more preferably 900° C. or less.
  • the present invention is not limited to the above-mentioned embodiment and can variously be changed within the scope of the present invention.
  • the ceramic layers 2 of a multilayer chip coil 1 a shown in FIG. 2 may be constituted by the ferrite composition of the above-mentioned embodiment.
  • the multilayer chip coil 1 a shown in FIG. 2 includes a chip body 4 a containing the ceramic layers 2 and internal electrode layers 3 a alternately laminated in the Z-axis direction.
  • Each of the internal electrode layers 3 a has a square ring shape, a C shape, or a U shape.
  • the internal electrode layers 3 a are spirally connected by a stepped electrode or a through hole electrode (not shown) for connecting internal electrodes going through the adjacent ceramic layers 2 and constitute a coil conductor 30 a.
  • Terminal electrodes 5 and 5 are formed on both ends of the chip body 4 a in the Y-axis direction and are connected with ends of leading electrodes 6 a located above and below in the Z-axis direction.
  • the terminal electrodes 5 and 5 are connected with both ends of the coil conductor 30 a forming a closed-magnetic-path coil.
  • the ceramic layers 2 and the internal electrode layers 3 are laminated in the Z-axis direction, and the end surfaces of the terminal electrodes 5 and 5 are parallel to the X-axis and the Z-axis.
  • the X-axis, the Y-axis, and the Z-axis are perpendicular to each other.
  • the winding axis of the coil conductor 30 a substantially corresponds to the Z-axis.
  • the winding axis of the coil conductor 30 is in the Y-axis direction (the longitudinal direction of the chip body 4 ).
  • the multilayer chip coil 1 shown in FIG. 1 can have a large winding number and is advantageous in easy achievement of high impedance up to high frequency band.
  • other features and effects are similar to those of the multilayer chip coil 1 shown in FIG. 1 .
  • the ferrite composition according to the present embodiment can be used for electronic components other than the multilayer chip coil shown in FIG. 1 or FIG. 2 .
  • the ferrite composition according to the present embodiment can be used as ceramic layers laminated along with a coil conductor.
  • the ferrite composition according to the present embodiment can be used for a composite electronic component formed by combining a coil, such as LC composite component, with other elements, such as capacitors.
  • the multilayer chip coil using the ferrite composition according to the present embodiment is used for any purposes, but is favorably used for, for example, a circuit where a winding-wire-type ferrite inductor is conventionally used so as to flow a particularly high AC current, such as a circuit of ICT devices (e.g., smart phones) using NFC technology, non-contact power supply, etc.
  • a winding-wire-type ferrite inductor is conventionally used so as to flow a particularly high AC current, such as a circuit of ICT devices (e.g., smart phones) using NFC technology, non-contact power supply, etc.
  • raw materials of a main component Fe 2 O 3 , NiO, CuO, and ZnO were prepared.
  • raw materials of a sub-component SiO 2 , Bi 2 O 3 , and Co 3 O 4 were prepared. Incidentally, the starting raw materials had an average grain size of 0.05 to 1.00 ⁇ m.
  • the obtained raw material mixture was dried and thereafter calcined in the air, and a calcined material was obtained.
  • the calcination temperature was appropriately selected from 500 to 900° C. according to the composition of the raw material mixture.
  • the calcined material was added with the balance of ZnO, which had not been mixed in the wet mixture step, and SiO 2 as a form of a compound of Zn 2 SiO 4 and was pulverized in a ball mill while further being added with other constituents of the sub-component or so. Then, a pulverized calcined material was obtained.
  • the amount of the balance of ZnO added to the calcined material was 1.0 to 3.0 times (in terms of mol) larger than the amount of SiO 2 added to the calcined material.
  • pulverized calcined material 100 parts by weight of the pulverized calcined material were added with 10.0 parts by weight of a polyvinyl alcohol aqueous solution (weight concentration: 6%) as a binder and were granulated to be granules. These granules were pressed to obtain a pressed body having a toroidal shape (size: outer diameter 13 mm ⁇ inner diameter 6 mm ⁇ height 3 mm) and a pressed body having a disk shape (size: outer diameter 12 mm ⁇ height 2 mm).
  • a polyvinyl alcohol aqueous solution weight concentration: 6%
  • the pressed bodies were fired in the air for two hours at 860 to 900° C., which is equal to or lower than the melting point of Ag (962° C.), and a toroidal core sample and a disk sample as sintered bodies were obtained. Moreover, the following characteristic evaluation was carried out for each of the obtained samples. Incidentally, an X-ray fluorescence analyzer confirmed that there was almost no change in composition between the weighed raw material powders and the fired pressed bodies.
  • In—Ga electrodes were applied on both surfaces of the disk sample, and a DC resistance value was measured to obtain a resistivity ⁇ (unit: ⁇ m). This measurement was carried out using an IR meter (4329A manufactured by HEWLETT PACKARD). In the present examples, a resistivity ⁇ of 1.0 ⁇ 10 6 ⁇ m or more (1.0.E+06 ⁇ m or more) was considered to be favorable.
  • a permeability ⁇ ′ of the toroidal core sample was measured using an RF impedance material analyzer (E4991A manufactured by Agilent Technologies). As the measurement conditions, the measurement frequency was 10 MHz, and the measurement temperature was 25° C. A permeability ⁇ ′ of 3.0 or more was considered to be favorable.
  • a copper wire was wound around the toroidal core sample by 30 turns, and a permeability ⁇ ′ at application of DC current was measured using an LCR meter (4284A manufactured by HEWLETT PACKARD).
  • the measurement frequency was 1 MHz, and the measurement temperature was 25° C.
  • the permeability was measured while the applied DC current was changed from 0 to 8 A and was graphed with the horizontal axis of DC current and the vertical axis of permeability. Then, an electric current value when the permeability decreased by 10% compared to 0 A of DC current was obtained as an Idc.
  • a density of the sintered ferrite composition was calculated from a size and a weight of the fired sintered body of the toroidal core sample. When the density was 4.40 g/cm 3 or more, sinterability was considered to be favorable.
  • the sintered ferrite compositions (toroidal core samples) were observed by an EPMA and a STEM-EDS.
  • the observation magnification was 20000 times or more and was appropriately determined depending on each of examples and comparative examples.
  • confirmed was whether or not each of the ferrite compositions contained a main phase composed of spinel ferrite phase, a first sub-phase composed of Zn 2 SiO 4 phase, a second sub-phase composed of SiO 2 phase, and a grain boundary phase composed of SiO 2 phase.
  • the area ratios of the main phases, the first sub-phases, the second sub-phases, and the grain boundary phases were calculated from the observation result by the STEM-EDS.
  • the first sub-phases had an area of 25% or more and 75% or less
  • the second sub-phases had an area of 0.1% or more and 15% or less
  • the main phases had an area of 25% or more and 55% or less
  • the grain boundary phases had an area of 0.01% or more and 5% or less.
  • An amount of Zn 2 SiO 4 was determined by measuring I B /I A of the sintered ferrite composition using an X-ray diffraction device (X'Pert PRO MPD CuK ⁇ line manufactured by Panarytical).
  • an AC resistance As for an AC resistance (Rac), a copper wire was wound around the toroidal core sample on the primary side by six turns and on the secondary side by three turns. During the measurement, the measurement frequency was 3 MHz, and the AC current value was 1.6 Arms.
  • a B-H analyzer SY-8218 manufactured by IWATSU ELECTRIC CO., LTD.
  • an amplifier (4101-IW manufactured by NF CORPORATION) were used.
  • An AC resistance Rac of 15.0 m ⁇ or less was considered to be favorable.
  • the amount of ZnO in the raw material mixture was increased compared to Sample No. 2, and SiO 2 and ZnO were added to the calcined material.
  • the compound of Zn 2 SiO 4 was not added.
  • the amount of ZnO in the raw material mixture was more than 10 mol %.
  • the amount of ZnO in the raw material mixture was increased compared to Sample No. 2, the compound of Zn 2 SiO 4 , SiO 2 , and if necessary, ZnO were added to the calcined material. Incidentally, the amount of ZnO in the raw material mixture was 10 mol % or less.
  • the amount of ZnO in the raw material mixture was increased compared to Sample No. 2, and the compound of Zn 2 SiO 4 and SiO 2 were added to the calcined material. Incidentally, the amount of ZnO in the raw material mixture was more than 10 mol %.

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